WO2015010304A1 - Nanocomposite hybride d'époxy-acrylique comprenant oxyde de zirconium pour des revêtements durcissables - Google Patents

Nanocomposite hybride d'époxy-acrylique comprenant oxyde de zirconium pour des revêtements durcissables Download PDF

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Publication number
WO2015010304A1
WO2015010304A1 PCT/CN2013/080129 CN2013080129W WO2015010304A1 WO 2015010304 A1 WO2015010304 A1 WO 2015010304A1 CN 2013080129 W CN2013080129 W CN 2013080129W WO 2015010304 A1 WO2015010304 A1 WO 2015010304A1
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composition
acrylic
monomer
methanol
epoxy
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PCT/CN2013/080129
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English (en)
Inventor
Peiqi Jiang
Liyi SHI
Dengsong ZHANG
Tingting YAN
Hongrui LI
Jian Zhao
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Essilor International (Compagnie Generale D'optique)
Shanghai University
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Application filed by Essilor International (Compagnie Generale D'optique), Shanghai University filed Critical Essilor International (Compagnie Generale D'optique)
Priority to JP2016528283A priority Critical patent/JP6143959B2/ja
Priority to EP13890203.6A priority patent/EP3024889A4/fr
Priority to PCT/CN2013/080129 priority patent/WO2015010304A1/fr
Priority to US14/908,046 priority patent/US9638834B2/en
Priority to CN201380078390.8A priority patent/CN105593294B/zh
Publication of WO2015010304A1 publication Critical patent/WO2015010304A1/fr

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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D135/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least another carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D135/02—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02C—SPECTACLES; SUNGLASSES OR GOGGLES INSOFAR AS THEY HAVE THE SAME FEATURES AS SPECTACLES; CONTACT LENSES
    • G02C7/00—Optical parts
    • G02C7/02—Lenses; Lens systems ; Methods of designing lenses
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • G—PHYSICS
    • G02—OPTICS
    • G02C—SPECTACLES; SUNGLASSES OR GOGGLES INSOFAR AS THEY HAVE THE SAME FEATURES AS SPECTACLES; CONTACT LENSES
    • G02C2202/00—Generic optical aspects applicable to one or more of the subgroups of G02C7/00
    • G02C2202/16—Laminated or compound lenses

Definitions

  • the inventions are in the field of hard coat materials, and more particularly to compositions and methods of preparing such coatings.
  • compositions, articles, and methods disclosed herein have applications in many fields, such as hard coats.
  • This disclosure focuses on applications on the ophthalmic field. More specifically, this disclosure focuses on methods of producing UV curable high refractive index (RI), clear, low-haze, coatings.
  • Hybrid epoxy-acrylic coatings provide good mechanical and optical properties.
  • Such hybrid formulations are used in optical coating applications, especially in UV-cured coatings for plastic ophthalmic lenses.
  • Zr0 2 zirconium dioxide
  • Zirconium dioxide has successively been dispersed in acrylic monomers or in epoxy monomers.
  • Zr0 2 colloids can be dispersed in either acrylic or epoxy monomers where the Zr0 2 nanoparticle surface is first functionalized, such as with silane compounds.
  • Dispersed Zr0 2 colloid in either acrylic or epoxy monomers can provide stable, clear fluids, capable of application to a surface, as a coating.
  • compositions comprising a high-index, Zr0 2 nanoparticle colloid coating solution in an epoxy-acrylic hybrid system for UV curable coating applications.
  • the composition can be used to form a curable composition, which can be coated onto a surface and then UV cured. Further, the compositions presented result in a low-haze coating on a polycarbonate (PC) lens after UV curing.
  • PC polycarbonate
  • a composition according to the invention includes: a continuous liquid phase comprising an acrylic monomer and an epoxy monomer; and a dispersed nano articulate comprising Zr0 2 modified with an acrylic silane; and wherein the composition is stable and transparent to visible light when coated on a lens.
  • a method according to the invention for forming or using the composition includes the steps of: mixing an acrylic silane and a methanol-based Zr0 2 sol to create a methanol-based silane-modified Zr0 2 sol; then mixing at least an acrylic monomer, an epoxy monomer, and the methanol-based silane-modified Zr0 2 sol to obtain the composition. Finally, the methanol solvent may be removed or left in, when necessary.
  • composition and methods can be adapted for use in coating onto another substrate, such as an ophthalmic lens.
  • an optical article comprising: an ophthalmic lens substrate; and a transparent, cured coating on the ophthalmic lens substrate, wherein the coating comprises: a continuous solid phase comprising an acrylic-epoxy copolymer; and a dispersed nanoparticulate of Zr0 2 modified with an acrylic silane.
  • compositions comprising a component does not exclude it from having additional components
  • an apparatus comprising a part does not exclude it from having additional parts
  • a method having a step does not exclude it having additional steps.
  • compositions, apparatuses, and methods that "consist essentially of or “consist of the specified components, parts, and steps are specifically included and disclosed.
  • the words “consisting essentially of,” and all grammatical variations thereof are intended to limit the scope of a claim to the specified materials or steps and those that do not materially affect the basic and novel character! stic(s) of the claimed invention.
  • Terms such as “first,” “second,” “third,” etc. may be assigned arbitrarily and are merely intended to differentiate between two or more components, parts, or steps that are otherwise similar or corresponding in nature, structure, function, or action.
  • the words “first” and “second” serve no other purpose and are not part of the name or description of the following name or descriptive terms.
  • the mere use of the term “first” does not require that there be any “second” similar or corresponding component, part, or step.
  • the mere use of the word “second” does not require that there be any "first” or “third” similar or corresponding component, part, or step.
  • first does not require that the element or step be the very first in any sequence, but merely that it is at least one of the elements or steps.
  • second does not necessarily require any sequence. Accordingly, the mere use of such terms does not exclude intervening elements or steps between the “first” and “second” elements or steps, etc.
  • a gel is a semi-solid, jelly-like physical state or phase.
  • the physical state of a gel is formed by a network of interconnected molecules, such as a crosslinked polymer or a network of micelles.
  • a gel is a dispersion in which both the network of molecules is continuous and the liquid is in a continuous phase.
  • a plastic material is any of a wide range of synthetic or semi-synthetic organic solids that are moldable. Plastics are typically organic polymers of high molecular mass, but they often contain other chemicals.
  • a "particle” refers to a body having a finite mass and sufficient cohesion such that it can be considered as an entity but having relatively small dimensions.
  • a particulate is a grouping of particles having similar chemical composition and particle size ranges anywhere in the range of about 5 nanometer (nanoparticles) up to 3 millimeters. Nanoparticles are normally considered to be particles having dimensions of in the range of up to about 100 nm. The nanoparticles can have a variety of shapes, such as, but not limited to, spherical, rod, plate, cube, triangular, hexagonal, and many others. In comparison, micro articles are particles that can have dimensions in the range of between about 100 nm and about 50,000 nm in size.
  • a dispersion is a system in which particles of a substance of one chemical composition and physical state are dispersed in another substance of a different chemical composition or physical state.
  • a heterogeneous dispersion is a "suspension” where the dispersed particles are larger than about 50 micrometers.
  • a heterogeneous dispersion is a "colloid” where the dispersed particles range up to about 50 micrometer (50,000 nanometers) in size.
  • modified or “derivative” means a chemical compound formed by a chemical process from a parent compound, wherein the chemical backbone skeleton of the parent compound is retained in the derivative.
  • water-based means that water is at least 10% by weight of the continuous phase of a fluid.
  • methanol-based means the methanol is at least 10% by weight of the continuous phase of a fluid.
  • silane refers to an organic chemical compound containing silicon, such as trichlorosilane (S1HCI 3 ) and tetramethyl silane (Si(CH 3 ) 4 ). Some silanes, such as alkoxy silanes, are highly reactive.
  • an "acrylic silane” is a silane that is also an acrylic compound that additionally contains an acryloyl group.
  • MPS 3-methacryloxypropyltrimethoxysilane
  • a "polymer” or “polymeric material” includes polymers, copolymers, terpolymers, etc.
  • copolymer as used herein is not limited to the combination of polymers having two monomelic units, but includes any combination of monomeric units, e.g., terpolymers, tetrapolymers, etc.
  • acrylic can refer to chemical compounds that contain an acryloyl group, which can be derived from acrylic acid, or to a polymerized product (e.g., a resin or plastic) formed with such an acrylic compound, and (meth)acrylic compounds.
  • epoxy can refer to chemical compounds that contain an epoxy group or a polymerized product (e.g., a resin or plastic) formed with such an epoxy compound.
  • DA 1173TM refers to 2-hydroxy-2-methyl-l-phenylpropane-l-one, which is a free-radical photo-polymerization initiator commercially available from Ciba Japan K.K, now part of BASF, also marketed under the tradename DAROCURE 1173TM.
  • UVI6976TM refers to a cationic photo-polymerization initiator containing a mixture of triarylsulfonium hexafluoroantimonate salts in propylene carbonate, which is commercially available from Dow Chemical.
  • EFKA3034TM is a fluorocarbon-containing organically modified polysiloxane, about 50 wt% active in a solvent of methoxypropanol, which is commercially available from BASF. It can be used as an additive to improve the wetting of the substrate and leveling of a coating.
  • resin encompasses synthetic substances of similar mechanical properties to natural resins, that is, highly viscous liquids that may harden into transparent solids.
  • a polycarbonate (PC) resin or plastic refers to any of a group of thermoplastic polymers containing carbonate groups. PC plastic is commonly used in ophthalmic products such as eyeglass lenses.
  • Allyl diglycol carbonate (ADC) plastic also known as "CR-39" is a plastic polymer of diethyl eneglycol bis allylcarbonate in presence of diisopropyl peroxydicarbonate ( ⁇ ) initiator and heat. A peroxide can also be used as an initiator. The presence of the allyl groups allows the polymer to form cross-links.
  • ADC is a thermosetting polymer.
  • ADC plastic is commonly used in the manufacture of eyeglass lenses.
  • a commercial example is ORMATM lenses available from Essilor International.
  • optical lens substrates or "optical base element” is understood to mean ophthalmic lenses and lenses for optical instruments; "ophthalmic lenses” are defined as lenses adapted namely for mounting in eyeglasses whose function is to protect the eye and / or to correct vision; these lenses are selected from the afocal, unifocal, bifocal, trifocal, and progressive lenses.
  • the substrate of the optical base element may be of thermosetting or thermoplastic nature.
  • the optical base element is made of a material classically used in optics and ophthalmology.
  • the materials are chosen from among the polycarbonates; polyamides; polyimides; polysulfones; copolymers of polyethylene there phthalate and polycarbonate; polyolefins, namely polynorbornenes; polymers and copolymers of diethylene glycol bis(allylcarbonate); (meth)acrylic polymers and copolymers, namely (meth)acrylic polymers and copolymers derived from bisphenol-A; thio(meth) acrylic polymers and copolymers; urethane and thiourethane polymers and copolymers; epoxy polymers and copolymers; and episulfide polymers and copolymers.
  • multifunctional monomer means a molecule that has more than one potential reactive site by which it can form inteimolecular chemical bonds.
  • the functionality of a monomer molecule is the number of functional groups which participate in the polymerization.
  • the multifunctional monomer can have, for example, 3 to 6 potential reactive sites or functionalities.
  • Such multifunctional monomers may be used in polymerizations to form branched or crosslinked chains.
  • a “piano" lens does not have an optical power for correcting vision.
  • optical properties of films and packaging material, clear or translucent specimens, and raw materials for paint and plastics can be differentiated by using the following measurement values: haze, clarity, and total transmittance.
  • An example of a laboratory instrument to objectively evaluate total appearance of transparent products is a HAZEGARD PLUS optical testing instrument, which is commercially available from BYK- Gardner.
  • transparent means having at least 80% transmittance to the full spectrum of visible light, which has a wavelength in the range of about 380 nm to about 740 nm.
  • transmittance is the ratio of transmitted light to total light directed through a medium at a particular wavelength or over a spectrum.
  • haze is the ratio of diffuse transmittance divided by total transmittance.
  • Zr0 2 nanoparticles can be dispersed in either solutions of acrylic or epoxy monomers (or in the respective resins of low-molecular weight polymers thereof) with the surface treatment agents (MPS or GPS for the respective monomers).
  • the surface treatment agents MPS or GPS for the respective monomers.
  • Zr0 2 microparticles can be used.
  • there is a compatibility issue whenever a solution or resin of an acrylic monomer with a dispersed MPS-modified Zr0 2 nanoparticulate is mixed with a solution or resin of an epoxy monomer with a dispersed GPS-modified Zr0 2 nanoparticulate.
  • the mixed solution forms a gel or becomes opaque.
  • Zr0 2 nanoparticles first functionalized with MPS are dispersed in a solution or resin of epoxy and acrylic monomers, haze is greatly reduced when coated on a surface of a PC lens.
  • compositions for dispersing Zr0 nanoparticles in a hybrid epoxy- acrylic monomer solution wherein the zirconium dioxide is functionalized with an acrylic silane.
  • the composition is a translucent liquid at room temperature.
  • the composition can be used to form a curable composition, which can be coated onto a surface and then UV cured. Further, the compositions presented result in a low-haze coating on a polycarbonate (PC) lens after UV curing.
  • a composition according to the invention includes: a continuous liquid phase comprising an acrylic monomer and an epoxy monomer; and a dispersed nanoparticulate comprising Zr0 2 modified with an acrylic silane; and wherein the composition is stable and transparent to visible light when coated on a lens.
  • composition and methods can be adapted for use in coating onto another substrate, such as an ophthalmic lens.
  • an optical article comprising: an ophthalmic lens substrate; and a transparent, cured coating on the ophthalmic lens substrate, wherein the coating comprises: a continuous solid phase comprising an acrylic-epoxy copolymer; and a dispersed nanoparticulate of Zr0 2 modified with an acrylic silane.
  • the methods for preparing a composition or optical article according to the invention includes the steps of: mixing an acrylic silane and a methanol-based Zr0 2 sol to create a methanol-based silane-modified Zr0 2 sol; then mixing at least an acrylic monomer, an epoxy monomer, and the methanol-based silane-modified Zr0 2 sol to obtain a composition comprising: a continuous liquid phase comprising an acrylic monomer and an epoxy monomer; and a dispersed nanoparticulate comprising Zr0 2 modified with an acrylic silane; and wherein the composition is stable and transparent to visible light when coated on a lens.
  • the methods can include a step of forming the methanol-based Zr0 2 sol.
  • the step of forming the methanol-based Zr0 2 sol comprises the step of: dialyzing a water-based Zr0 2 sol in a methanol bath.
  • the step of mixing the acrylic silane and the methanol-based Zr0 2 sol further comprises mixing under agitation at a temperature below 30 °C to form a sol or a suspension.
  • the acrylic silane is 3-methacryloxypropyltrimethoxysilane ("MPS").
  • MPS 3-methacryloxypropyltrimethoxysilane
  • Other examples of an acrylic silane that can be used according to the invention are selected from the group consisting of: 3-(methacryloyloxy)propyltrimethoxysilane,
  • the molar ratio of the acrylic silane to Zr0 2 is in the range of 0.1 : 1 to 0.2: 1. Without being limited by any hypothesis, it is believed that the silane functionality reacts or interacts with the surface of the Zr0 2 .
  • the mole ratio of the acrylic monomer to the epoxy monomer is in the wt% range of approximately 10:90 to 90: 10.
  • the acrylic monomer is 1,6-hexandiol diacrylate (HDD A).
  • an acrylic monomer that can be used according to the invention are selected from the group consisting of: difunctional (meth)acrylate monomers, trifunctional acrylic monomers, multifunctional (meth)acrylic monomer(s), poly(meth)acrylate monomers, such as pentaerythritol triacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetraacrylate, glycerol triacrylate, 1,2,4-butanetriol trimethacrylate, propoxylated trimethylolpropane triacrylate, propoxylated glyceryl triacrylate, tris(2-hydroxy ethyl)isocyanurate triacrylate, ethoxylated trimethylolpropane triacrylate, di-trimethylolpropane tetraacrylate, dipent
  • the polyol poly(meth)acrylate monomers may be chosen from: pentaerythritol tri- and/or tetraacrylate, dipentaerythritol hexaacrylate, polyol poly(meth)acrylate monomers, polyurethane poly(meth)acrylate monomers, and any combination thereof. It should be understood that the acrylic monomers can be partially pre-polymerized.
  • the epoxy monomer is 1,4-butanediol diglycidyl ether (BDDGE).
  • BDDGE 1,4-butanediol diglycidyl ether
  • Other examples of an epoxy monomer that can be used according to the invention are selected from the group consisting of: difunctional epoxy monomers, trifunctional epoxy monomers, multifunctional epoxy monomers, polyol polyglycidyl ether monomers, such as trimethylolmethane triglycidyl ether, trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether, triphenylolmethane triglycidyl ether, trisphenol triglycidyl ether, tetraphenylol ethane triglycidyl ether, tetraglycidyl ether of tetraphenylol ethane, p-aminophenol triglycidyl
  • the dispersed nanoparticulate can be in the range of 10 to 70 wt% of the wet composition. Preferably, the dispersed nanoparticulate is in the range of 30 to 60 wt% of the composition.
  • the methods preferably further include a step of removing partially or essentially all the methanol from the composition.
  • the step of removing partially or essentially all the methanol from the composition can include a step of rotary evaporation.
  • the methods can include a step of forming the composition with at least one photo-polymerization initiator for polymerizing the aciylic and epoxy monomers.
  • the photo-polymerization initiator is selected from the group consisting of: 2-hydroxy- 2-methyl-l-phenylpropane-l-one, a triarylsulfonium hexafluoroantimonate salt, haloalkylated aromatic ketones such as chloromethylbenzophenones; some benzoin ethers such as ethyl benzoin ether and isopropyl benzoin ether; dialkoxyacetophenones such as diethoxyacetophenone and a, a-dimethoxy-a-phenylacetophenone; hydroxy ketones such as (1- [4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-l-propan-l-one-) (Irgacure® 2959 from CIBA), 1-hydroxy
  • a mixture which may be used in one embodiment of this invention comprises Darocur® 1173 with Irgacure® 819, in a weight ratio of Darocur® 1173 to Irgacure® 819, which may range from 75:25 to 85:15, for instance of about 80:20.
  • free-radical initiator blends such as Genocure® LTM sold by RAHN USA CORP., may be used.
  • Useful cationic initiators for the purpose of this invention include the aromatic onium salts, including salts of Group Va elements, such as phosphonium salts, e.g., triphenyl phenacylphosphonium hexafluorophosphate, salts of Group Via elements, such as sulfonium salts, e.g., triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphate (such as Cyracure® UVI-6992 sold by DOW CHEMICALS) and triphenylsulfonium hexafluoroantimonate (such as Cyracure® UVI-6976 sold by DOW CHEMICALS), and salts of Group Vila elements, such as iodonium salts, e.g., diphenyliodonium chloride.
  • salts of Group Va elements such as phosphonium salts, e.g., triphenyl phenacy
  • cationic initiators can also be used in addition to those referred to above; for example, the phenyldiazonium hexafluorophosphates containing alkoxy or benzyloxy radicals as substituents on the phenyl radical as described in U.S. Pat. No. 4,000,115, the disclosure of which is incorporated herein by reference.
  • Preferred cationic initiators for use in the compositions of this invention are the salts of Group Via elements and especially the sulfonium salts.
  • a preferred mixture comprises Cyracure® UVI-6992 with Cyracure® UVI- 6976, in a weight ratio of UVI®-6976 to UVI®-6992 which may range from 70:30 to 80:20, for instance about 75:25.
  • the photo-polymerization initiator is in the range of 1 to 6 wt% of the monomers in the continuous liquid phase of the composition.
  • this step of forming can be as simple as mixing, either together or separately from another mixing step.
  • the polymerizing can be induced by UV polymerization, followed by drying the composition or suspension into a resulting layer on the lens.
  • the methods can include a step of forming the composition with a surfactant.
  • the surfactant is a fluorocarbon-containing organically modified polysiloxane.
  • the surfactant is in the range of 0.05 to 0.5 wt% of the monomers in the continuous liquid phase of the composition.
  • this step of forming can be as simple as mixing, either together or separately from another mixing step.
  • a method according to the invention can additionally include a step of coating the composition onto an ophthalmic lens to obtain a coated lens.
  • the step of coating can further include a step of spinning the ophthalmic lens substrate according to methods known to those of skill in the art.
  • the methods can further include a step of UV curing the coating of the composition onto the ophthalmic lens.
  • the composition should be adapted to be a UV-curable composition, for example, by including a photo-polymerization initiator.
  • the ophthalmic lens can comprise a plastic selected from the group consisting of: polycarbonate (PC), allyl diglycol carbonate (ADC), diethylene glycol diallyl carbonate, allyl diglycol carbonates, allylic esters, acrylic esters, acrylates, methyl, allyl and butyl methacrylates, polycarbonates, styrenics, polyesters, allyl diglycol carbonates, triallyl cyanurate, triallyl phosphate, triallyl citrate, diallyl phenyl phosphonate, urethanes, epoxies and silicones, acrylic high index materials, thiol-polyurethane materials, high index lens materials, such as 1.6 Thin & Light lens, 1.67 Thin & Light lens made by polyurethane materials, and 1.74 Thin and Light lenses made by epi-thio materials.
  • PC polycarbonate
  • ADC allyl diglycol carbonate
  • diethylene glycol diallyl carbonate ally
  • GPS 3-glycidoxypropyltrimethoxysilane
  • Example 1 MPS-modified Zr0 2 in acr lic-epox monomers
  • a mixture of between about 30wt%:70wt% to about 70wt%:30wt% of 1,6-hexandiol diacrylate (HDDA) and 1,4 butanediol diglycidyl ether (BDDGE) was slowly added into the methanol-based MPS-modified Zr0 2 sol with stirring.
  • a mixture (50:50 wt%) of 1,6-hexandiol diacrylate (HDDA) and 1,4- butanediol diglycidyl ether (BDDGE) was slowly added into the methanol-based MPS-modified Zr0 2 sol with stirring.
  • the methanol-based mixture was concentrated by a rotary evaporator at a temperature lower than 30° C to remove essentially all of the methanol solvent.
  • the solvent solubilizes the epoxy monomers and acrylic monomers and suspends the silane-modified Zr0 2 particles.
  • suitable solvents may be used as well.
  • the solvent may be left in any of the compositions disclosed herein, so that such compositions may further comprise at least one solvent.
  • a colloidal composition consisting essentially of a continuous liquid phase of epoxy and acrylic monomers with a dispersed nanop articulate of MPS-modified Zr0 2 was obtained.
  • the MPS-modified Zr0 2 in the concentrated composition was about 30 wt%.
  • the UV-curable composition was then coated onto a PC piano lens and an ADC piano lens by a spin technique at 500 rpm for 10 seconds and then 1,000 rpm for 10 seconds.
  • the coated lenses were cured by UV fusion lamp.
  • the lens with these cured coatings showed very good optical properties, as reported in Table 1.
  • HDDA 1,6-Hexandiol diacrylate
  • MPS-modified Zr0 2 sol with stirring Then the mixture was concentrated by a rotary evaporator at the temperature lower than 30 °C to remove the methanol. After concentration, a colloidal composition consisting essentially of a continuous liquid phase of acrylic monomer with a dispersed nanoparticulate of MPS-modified Zr0 2 was obtained. The MPS-modified Zr0 2 in the concentrated composition was about 30 wt%. This composition is referred to as "HDDA/MPSZr0 2 ".
  • BDDGE 1,4-Butanediol diglycidyl ether
  • UV-curable composition 15 grams of this colloidal composition was mixed with UVI-6976 photo- polymerization initiator (6 wt%) and EF A3034TM surfactant (0.2 wt%) to obtain a UV-curable composition.
  • the UV-curable composition was then coated onto a PC piano lens and an ADC piano lens by a spin technique at 500 rpm for 10 seconds and then 1,000 rpm for 10 seconds.
  • the coated lenses were cured by UV fusion lamp.
  • the obtained ACD lens showed very good optical properties, but the obtained PC lens showed a high haze value, as reported in Table 1.
  • BDDGE/GPSZr0 2 from Comparative Example 3 were mixed with DAR1 173TM photo- polymerization initiator (3 wt%) and UVI6976TM photo-polymerization initiator (3 wt%) and EF A3034TM surfactant (0.2 wt%).
  • the mixture gelled very quickly and was not a usable composition for use in coating of optical articles such as lenses, as reported in Table 1.
  • Example 1 was repeated except the silane was GPS (3- glycidoxypropyltrimethoxysilane) instead of MPS (3-methacryloxypropyl trimethoxysilane).
  • the methanol-based mixture was concentrated by a rotary evaporator at a temperature lower than 30 °C to remove essentially all of the methanol solvent.
  • suitable solvents such as, but not limited to, ethanol, isopropanol, and water.
  • a gel-like composition was obtained, which was not suitable for use in coating of optical articles such as lenses, as reported in Table 1.
  • Table 1 Exam les of modified ZrO? com atibilit with monomers
  • the present invention is well adapted to attain the ends and advantages mentioned as well as those that are inherent therein.

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  • Epoxy Resins (AREA)

Abstract

L'invention concerne une composition comprenant : une phase liquide continue comprenant un monomère acrylique et un monomère époxy; et une nanoparticule dispersée comprenant du ZrO2 modifié par un silane acrylique; et dans laquelle la composition est transparente à la lumière visible lorsque revêtue sur une lentille. De plus, l'invention concerne un procédé comprenant les étapes de : mélange d'un silane acrylique et d'un sol ZrO2 à base de méthanol pour créer un sol ZrO2 à base de méthanol, modifié avec du silane; puis mélange d'au moins un monomère acrylique, d'un monomère époxy, et du sol ZrO2 à base de méthanol modifié avec du silane pour obtenir la composition. La composition peut être adaptée au revêtement et au durcissement sur un autre substrat, tel qu'une lentille ophtalmique.
PCT/CN2013/080129 2013-07-25 2013-07-25 Nanocomposite hybride d'époxy-acrylique comprenant oxyde de zirconium pour des revêtements durcissables WO2015010304A1 (fr)

Priority Applications (5)

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JP2016528283A JP6143959B2 (ja) 2013-07-25 2013-07-25 硬化性コーティング用の酸化ジルコニウムナノ複合体含有エポキシ−アクリルハイブリッド
EP13890203.6A EP3024889A4 (fr) 2013-07-25 2013-07-25 Nanocomposite hybride d'époxy-acrylique comprenant oxyde de zirconium pour des revêtements durcissables
PCT/CN2013/080129 WO2015010304A1 (fr) 2013-07-25 2013-07-25 Nanocomposite hybride d'époxy-acrylique comprenant oxyde de zirconium pour des revêtements durcissables
US14/908,046 US9638834B2 (en) 2013-07-25 2013-07-25 Hybrid epoxy-acrylic with zirconium oxide nanocomposite for curable coatings
CN201380078390.8A CN105593294B (zh) 2013-07-25 2013-07-25 用于可固化涂层的混合环氧‑丙烯酸与氧化锆纳米复合材料

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PCT/CN2013/080129 WO2015010304A1 (fr) 2013-07-25 2013-07-25 Nanocomposite hybride d'époxy-acrylique comprenant oxyde de zirconium pour des revêtements durcissables

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JP (1) JP6143959B2 (fr)
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WO (1) WO2015010304A1 (fr)

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JP7567789B2 (ja) * 2019-06-18 2024-10-16 住友電気工業株式会社 樹脂組成物、光ファイバのセカンダリ被覆材料、光ファイバ及び光ファイバの製造方法
WO2022060657A1 (fr) 2020-09-15 2022-03-24 Saudi Arabian Oil Company Procédés de fabrication de fluides de fracturation hydraulique et leur utilisation
CN114250020B (zh) * 2021-12-29 2022-08-09 山东玉马遮阳科技股份有限公司 一种丙烯酸涂层及其制备方法和应用、固化物、户外建筑

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JP6143959B2 (ja) 2017-06-07
CN105593294B (zh) 2017-05-17
US9638834B2 (en) 2017-05-02
EP3024889A1 (fr) 2016-06-01
CN105593294A (zh) 2016-05-18
US20160161643A1 (en) 2016-06-09
JP2016527350A (ja) 2016-09-08

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